Self-assembly of soft-matter quasicrystals and their approximants

Proc Natl Acad Sci U S A. 2011 Dec 27;108(52):20935-40. doi: 10.1073/pnas.1019763108. Epub 2011 Dec 12.

Abstract

The surprising recent discoveries of quasicrystals and their approximants in soft-matter systems poses the intriguing possibility that these structures can be realized in a broad range of nanoscale and microscale assemblies. It has been theorized that soft-matter quasicrystals and approximants are largely entropically stabilized, but the thermodynamic mechanism underlying their formation remains elusive. Here, we use computer simulation and free-energy calculations to demonstrate a simple design heuristic for assembling quasicrystals and approximants in soft-matter systems. Our study builds on previous simulation studies of the self-assembly of dodecagonal quasicrystals and approximants in minimal systems of spherical particles with complex, highly specific interaction potentials. We demonstrate an alternative entropy-based approach for assembling dodecagonal quasicrystals and approximants based solely on particle functionalization and shape, thereby recasting the interaction-potential-based assembly strategy in terms of simpler-to-achieve bonded and excluded-volume interactions. Here, spherical building blocks are functionalized with mobile surface entities to encourage the formation of structures with low surface contact area, including non-close-packed and polytetrahedral structures. The building blocks also possess shape polydispersity, where a subset of the building blocks deviate from the ideal spherical shape, discouraging the formation of close-packed crystals. We show that three different model systems with both of these features-mobile surface entities and shape polydispersity-consistently assemble quasicrystals and/or approximants. We argue that this design strategy can be widely exploited to assemble quasicrystals and approximants on the nanoscale and microscale. In addition, our results further elucidate the formation of soft-matter quasicrystals in experiment.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Colloids / chemistry*
  • Computer Simulation
  • Crystallization / methods*
  • Micelles*
  • Models, Molecular
  • Nanostructures / chemistry*
  • Thermodynamics

Substances

  • Colloids
  • Micelles